1. Field of the Invention
The present invention relates to novel quaternary ammonium compounds, and more particularly to monomeric polyquaternary ammonium derivatives of substituted dipropylene triamine, their process of manufacture, their use in hair care products and in the treatment of fibers and textiles, and preparations containing the quaternary ammonium compounds.
The novel quaternary ammonium compounds of the invention have very high substantivity to fibers such as wool fiber, acrylic fibers, human hair and textiles made of wool and acrylic fibers or mixed fibers, with excellent conditioning and softening effects. By xe2x80x9cmixed fibersxe2x80x9d is meant a combination of polyester and cotton or rayon fibers, or polyester and wool fibers.
2. Description of the Related Art
Quaternary ammonium compounds are known for a variety of different applications.
U.S. Pat. Nos. 2,654,785 and 2,668,854 to Miescher discloses wholly or partially quaternated azalkane diamines. The quaternary ammonium compounds may be used as medication. The patent further discloses use of diethyl sulfate as a quaternating agent.
U.S. Pat. No. 4,126,562 to Goffinet et al. discloses non-ionic textile softening compositions comprising a cationic surfactant and a non-ionic fabric-conditioning substance selected from fatty acid esters of mono-or polyhydric alcohols having from 1 to 8 carbon atoms and anhydrides thereof. The composition may additionally comprise an insoluble cationic softener selected from di-C10-C22 alkyl quaternary ammonium salts and C8-C25 imidazolinium salts.
U.S. Pat. No. 4,250,112 to Lobach et al. discloses polyalkylenepolyamines containing quaternary dialkylammonium groups and their use as agents for retention of fibers in the manufacture of papers.
U.S. Pat. No. 4,997,912 to Wirtz et al. discloses esters of oxalkylated alkylalkylenediamines, which may be quaternized, obtained by esterifying oxyalkylated alkylalkylenediamines. The compounds are used as corrosion inhibitors in crude oil recovery and treatment plants.
U.S. Pat. No. 4,157,388 to Christiansen discloses polycationic or polyquaternary ammonium ionenes, which generally are hygroscopic. The compounds are useful as conditioning agents for skin, hair and textile products.
U.S. Pat. No. 4,720,383 to Drach et al. discloses imidazolinium compounds used for softening and conditioning fibers, hair and skin. The patent discloses that it is known to prepare softeners comprising quaternaries of ethoxylated or nonethoxylated amido amines derived from the reaction of high molecular weight acid like stearic and a multi amine such as diethylenetriamine. The standard alkylating agents are diethyl sulfate or dimethyl sulfate.
U.S. Pat. No. 4,764,306 to Login discloses a process for the production of bis-quaternary ammonium compounds comprising contacting a tertiary amine with a neutralizing acid, such as HCL, and subsequently contacting the resulting mixture with an epoxide, preferably epihalohydrin or epichlorohydrin. The tertiary amine is preferably stearlyl dimethyl amine or lauryl dimethyl amine. The resulting bis-quaternary ammonium compounds are incorporated into hair conditioners.
U.S. Pat. No. 4,808,321 to Walley discloses liquid fabric softening and antistatic compositions which contain mono-ester analogs of ditallow, dimethyl ammonium chloride.
U.S. Pat. No. 4,913,828 to Caswell et al. discloses alkyl amine-anionic surfactant ion-pair/wax composites useful as fiber, hair and fabric conditioning agents.
U.S. Pat. Nos. 5,087,733 and 5,206,013 to Deppert et al. disclose sulfur containing quaternary ammonium compounds, and their use as hair conditioning agents.
U.S. Pat. No. 5,254,271 to Hamann et al. discloses hair and fabric conditioning compositions comprising mixtures of quaternary ammonium compounds with or without ester groups prepared by reacting amines with dimerized fatty acids and subsequent quaternization or protonation with inorganic or organic acids.
U.S. Pat. Nos. 5,427,773; 5,427,774; and 5,451,394 to Chaudhuri et al. discloses non-irritating, hair, skin and textile substantive, quaternary ammonium salts of paradialkylamino benzamides. These benzamide derivatives are also active sunscreening agents.
U.S. Pat. No. 5,863,526 to Yeung et al. discloses a hair conditioning composition comprising homopolymers prepared from ammonium quaternary salts of amino alkylacrylamides.
U.S. Pat. No. 5,916,863 to Iacobucci et al. discloses a textile softening agent comprising a quaternary ammonium salt which comprises a mixture of mono-, di-, and tri-ester components, having high diester content and low triester content.
The references describe the production of cationic and quaternary ammonium compounds and their use in the treatment of hair, fiber and textiles as softening and conditioning agents. However, none of the references disclose or suggest the specific, novel quaternary ammonium compounds of the invention, a process of preparing same, or the use of such compounds in the treatment of fibrous materials.
Additionally, the substantivity characteristics of the quaternary ammonium compounds of the invention are superior to known quaternary ammonium compounds, and are stable in highly acidic or highly alkaline medium. These properties make the quaternary ammonium compounds of the invention suitable for use in specialized alkaline fiber or hair treatment systems such as in hair straightening treatments, at a high pH of 12.00, and also in permanent waving, at a pH of 9-10. The quaternary ammonium compounds of the invention are stable to these extreme pH conditions. The quaternary ammonium compounds of the invention also have very high substantivity to fibers such as wool fiber, acrylic fibers, human hair and textiles made of wool and acrylic fibers or mixed fibers, with excellent conditioning and softening effects, as shown in Examples 52 and 53 below.
It is an object of the present invention to provide a process for producing quaternary ammonium compounds which are very mild.
It is another object of the invention to provide a process for making quaternary ammonium compounds for use in the treatment of hair, fiber and textile materials.
It is yet another object of the invention to provide a process for making quaternary ammonium compounds for use in hair care products that allow the use and application of thio-based hair treatment specialties and formulations.
It is a further object of the invention to provide a process for making quaternary ammonium compounds which have very high substantivity to fibers such as wool fiber, acrylic fibers, human hair, and textiles made of wool and acrylic fibers or mixed fibers.
Yet another object of the invention is to provide a method for producing quaternary ammonium compounds for use in hair shampoo products which have excellent conditioning effects when used alone or in combination with other surfactants.
Another object of the invention is to provide a method of producing quaternary ammonium compounds which are stable in highly acidic or highly alkaline medium.
It is another object of the invention to provide quaternary ammonium compounds which are excellent conditioners and softeners for fibrous materials.
Yet another object of the invention is to provide quaternary ammonium compounds which are suitable for use in alkaline fiber or hair care systems such as hair straighteners and permanent wave treatments.
These and other objects are accomplished by providing a process for preparing quaternary ammonium compounds, and specifically monomeric, multi-charge, multi-functional quaternary ammonium compounds. These quaternary ammonium compounds are improved as compared to commercially available quaternary ammonium compounds, as they are milder and less irritating to the skin and eyes. Hair care formulations containing the quaternary ammonium compounds of the invention are conditioning and emollient, have very low toxicological profiles, and are not irritating to the skin and eyes.
The novel quaternary ammonium compounds of this invention have unique properties in that they have very high substantivity to fibers such as wool fiber, acrylic fibers, human hair and textiles made of wool and acrylic fibers or mixed fibers. Such high substantivity is a useful property for allowing the application of these compounds to fibers, and especially to human hair. The utility of such compounds in hair care products results in excellent conditioning and softening effects. The high substantivity of these novel quaternary ammonium compounds to hair, fibers, and textiles, and their mildness to the skin and eyes, make them well suited for softening and conditioning fibers for applications such as personal care, laundry, and textile use.
The novel quaternary ammonium compounds of the invention are preferably prepared by:
1. Reacting an Amine with alkoxide, preferably Propylene Oxide (xe2x80x9cPOxe2x80x9d), yielding a polyoxypropylene adduct amine of alkoxide (hereinafter abbreviated xe2x80x9cAMPxe2x80x9d). The alkoxide is selected from the group consisting of propylene oxide, ethylene oxide, and a mixture of propylene oxide and ethylene oxide.
2. Reacting the adduct AMP of step 1 with a 1,2 epoxyalkane having from 3 to 28 carbon atoms (such as xcex1-olefin epoxide, i.e., C16-Epoxide) to produce the oxyalkylated condensate;
3. Further quaternizing the hydroxyalkylated condensate of step 2 with a suitable quaternization agent, preferably diethyl sulfate (xe2x80x9cDESxe2x80x9d) or dimethyl sulfate (xe2x80x9cDMSxe2x80x9d), to produce a quaternary ammonium compound.
4. Optionally diluting the quaternary ammonium compound produced in Step 3 in water to obtain the desired concentration, preferably a 25% or 50% or 75% solids-liquid solution or dispersion.
The process of the invention provides a composition of matter comprising a monomeric polyquaternary ammonium derivative of an amine, preferably a substituted, dipropylene triamine. The preferred, highly substituted, dipropylene triamine which is used in the process of the invention is Tetramethyliminobis-Propylamine, abbreviated herein as xe2x80x9cAMxe2x80x9d. The propoxylation (or ethoxylation) step adds multiple units of oxypropyl or oxyethyl chains. This propoxylated adduct is then reacted with of C16-xcex1-olefin epoxide (preferably one mole) to produce the oxyalkylated condensate, i.e., hydroxycetoxy-polyoxypropylated tetramethyliminobis propylamine. This hydroxycetoxy-polyoxproplylated tetramethyliminobis propylamine is then further quaternized with 3 moles of Diethyl Sulfate to yield a quaternary of this invention. The preferred molar ratio is 1:2 to 1:3 for full quaternization. The preferred molar ratio is 1:3.
The very mild quaternary ammonium compounds of the invention are particularly useful in fiber treatment, especially in hair treatment compositions that permit the application of thio-based hair treatments, and are suitable for use in alkaline fiber or hair care systems such as hair straighteners and permanent wave treatments. The quaternary ammonium compounds of the invention may be used in shampoos, conditioners, and conditioning shampoos. When the quaternary ammonium compounds of the invention are deposited on human hair, they improve the ability of the hair to be combed and provide an antistatic effect. This makes the hair more manageable.
The compounds of the present invention are generally semi-liquids at room temperatures. They mix and dissolve and disperse readily with most types of shampoo/conditioner formulations.
The quaternary ammonium compounds of the invention are excellent hair-conditioning agents, as stated above. They are also general antistats and humectants for fibrous textile products such as rayon and fiber glass, and anti-static agents for textile and rug products in general. The compounds of the invention are also effective as wash cycle conditioners and rewetting agents in some laundry detergent formulations. Thus, the quaternary ammonium compounds of the invention find application in compositions such as fabric detergent, shampoos, hair conditioners, and dryer- and washer-added fabric conditioners.
The foregoing list is only exemplary of the type of compositions in which the novel quaternary ammonium compounds of this invention may be used, and, as such, is not to be considered limiting.
The preferred, highly substituted, dipropylene triamine which is used in the process of the invention is Tetramethyliminobis-Propylamine, abbreviated herein as xe2x80x9cAMxe2x80x9d, whose structure is: 
The propoxylation (or ethoxylation) step adds multiple units of oxypropyl(or oxyethyl chains) and produces a compound having the chemical name Poly(hydroxypropyl) Tetramethyliminobis propylamine, which has the following structure: 
where
Rxe2x95x90H (ethoxylated derivative);
Rxe2x95x90CH3 (propoxylated derivative); and
n=1 to 100 moles of Ethylene Oxide (xe2x80x9cEOxe2x80x9d) and/or Propylene Oxide (xe2x80x9cPOxe2x80x9d).
Specifically, it is preferred to form a 3 mole Propoxylate of AM, abbreviated herein as AMP-3, having the chemical name Tri(oxypropyl) Tetramethyliminobis propylamine, and having the following structure: 
Alternatively, it is preferred to form a 5 mole Propoxylate of AM, abbreviated herein as AMP-5, having the chemical name Pentaoxypropyl-Tetramethyliminobis propylamine, which has the following structure: 
This propoxylated adduct is then reacted with a 1,2 epoxyalkane having from 3 to 28 carbon atoms, preferably with one mole of C16-xcex1-olefin epoxide (abbreviated herein as xe2x80x9cC16-Epoxidexe2x80x9d), also known as 1,2-epoxycetane, or 1,2-epoxyhexadecane, which has the following structure: 
to produce a oxyalkylated condensate, namely, a hydroxycetylalkylated condensate of propxylated or ethoxylated tetramethyliminobis propylamine, which has the following structure: 
where
Rxe2x95x90H (ethoxylated derivative);
Rxe2x95x90CH3 (propxylated derivative); and
n=1 to 100 moles of EO and/or PO.
Specifically, AMP-3 is reacted with C16-Epoxide to produce Tri(oxypropyl)-xcfx89-hydroxycetyl-Tetramethyliminobis Propylamine, abbreviated herein as AMP-3-CT. AMP-5 is reacted with C16-Epoxide to produce Penta(oxypropyl)-xcfx89-hydroxycetyl-Tetramethyliminobis Propylamine.
Alternatively, AMP-3 may be reacted with 1,2-Epoxydodecane/1,2-Epoxytetradecane to produce Tri(oxypropyl)-xcfx89-hydroxy(lauryl/myristyl)-Tetramethyliminobis propylamine, abbreviated herein as AMP-3-LM, which has the following structure: 
The hydroxyalkoxy-polyoxyalkoxylated tetramethyliminobis propylamine is then quaternized with a quaternizing agent, preferably 3 moles of Diethyl Sulfate having the formula (C2H5)2SO4, to yield a quaternary ammonium compound of this invention, having the following generic structure: 
Specifically, the hydroxycetoxy-tri(oxypropylated) tetramethyliminobis propylamine is quaternized with Diethyl Sulfate having the formula (C2H5)2SO4, to yield a quaternary ammonium compound of this invention, having the following structure: 
This quaternary ammonium compound has the trade name FINQUAT(copyright) CT-P (INCI Name: Quaternium 89), and the chemical name: Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-Triethyl, Nxe2x80x2,Nxe2x80x2,Nxe2x80x2xe2x80x3,Nxe2x80x2xe2x80x3-Tetramethyl, Nxe2x80x3-[(Trioxypropyl)-xcfx89-hydroxycetyl], dipropylene triammonium triethosulfate.
Quaternating agents such as alkyl or alkenyl halides, such as methyl chloride, methyl bromide or methyl iodide, or other dialkyl sulfates such as di-methyl sulfate may be used. The molar ratio of the oxyalkylated condensate to the quaternating agent is in the range of 1:2 to 1:3, with a 1:3 ratio being preferred.
This invention is also directed to the use of the quaternary ammonium compound produced by the method of the invention in treating hair, fiber, and textile materials. The quaternary compounds of the invention are particularly useful in fiber treatment, especially in hair treatment compositions that permit the application of thio-based hair treatments.
More particularly, the compounds of the invention may be obtained by the following method:
A. Starting with 1 mole of tetramethyliminobis propylamine.
B. Adding to the compound of Step A from 1 to 100 moles of alkoxide, preferably either ethylene oxide or propylene oxide, or a mixture of ethylene oxide and propylene oxide, in any ratio.
C. Reacting each mole of the compound produced in Step B with from 0.90 to 1.0 mole of a 1,2 epoxyalkane having from 3 to 28 carbon atoms, preferably C16-xcex1-olefin-Epoxide.
D. Quaternizing each mole of the compound produced in Step C with 2.5 to 3.00 moles of a suitable quaternization agent, such as diethyl sulfate or dimethyl sulfate.
E. Optionally diluting the quaternary compound produced in Step D in water to obtain the desired concentration, preferably a 25%-75% solids-liquid solution or dispersion, and most preferably a 70% concentration.
The quaternary ammonium compounds of the invention are poly-functional with 3 quaternary positions per mole of the molecule. This high density of quaternized nitrogens on the molecule allows the molecule to reach and attach to the anionic hair or fibers. Such an attachment offers antistatic effects besides being beneficial as conditioners and softeners. Furthermore, the feel imparted to hair and fibers/textiles is soft and oil free which is also an advantageous quality of the quaternary ammonium compounds of the invention.
The quaternary ammonium compounds of this invention may be used in treatment of hair, textiles and fabrics. The amount used in such applications is dependent on the type of compositions, the type and quantity of other ingredients used, and the amount and type of functional additives that are utilized.
Further, the quaternary ammonium compounds of this invention possess other unusual physio-chemical properties, which can make them beneficial and unique components of sophisticated treatment systems. Thus, the quaternary ammonium compounds described herein may serve not only as hair, textile and fiber treatment agents, but may also exhibit one or more other functions, such as adsorption on anionically charged particulate matter as in clays, pigments, etc.
The quaternary ammonium compounds have shown usefulness similar to conventional quaternary ammonium compounds with the additional benefits of being mild to the skin. Also, skin feel is even better than using conventional quaternary ammonium compounds. In a specific embodiment, and by way of illustration, this invention contemplates the production of the following quaternary ammonium compounds:
1. Quaternary P3CT, Trade Name: FINQUAT CT-P (INCI Name: Quaternium 89) whose structure is set forth above and whose chemical name is Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-Triethyl, Nxe2x80x2,Nxe2x80x2,Nxe2x80x2xe2x80x3,Nxe2x80x2xe2x80x3-Tetramethyl, Nxe2x80x3-[(Trioxypropyl)-xcfx89-hydroxycetyl], dipropylene triammonium triethosulfate.
2. Quaternary P5CT, chemical name: Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-Triethyl, Nxe2x80x2,Nxe2x80x2,Nxe2x80x2xe2x80x3,Nxe2x80x2xe2x80x3-Tetramethyl, Nxe2x80x3-[(Pentaoxypropyl)-xcfx89-hydroxycetyl], dipropylene triammonium triethosulfate, and whose structure is: 
3. Quaternary P3LM, chemical name: N,N,N-Triethyl, Nxe2x80x2,Nxe2x80x2,Nxe2x80x2xe2x80x3,Nxe2x80x2xe2x80x3-Tetramethyl, Nxe2x80x3-[(Trioxypropyl),-xcfx89-hydroxylauryl/myristyl], dipropylene triammonium triethosulfate, whose structure is: 
Some of these quaternary ammonium compounds are used in hair care formulations. Hair care formulations prepared according to the invention, which contain the quaternary ammonium compounds added thereto, can be formed, without limitation, into applications such as solutions, emulsions, gels, solids, emulsions, aerosols, powders, creams, granules, or tablets.
Mildness and emolliency of these quaternary ammonium compounds is of importance to the improved hair care products including the quaternary ammonium compounds of the invention. One major aspect of quaternary ammonium compounds of this invention is their very, very low to negligible toxicological effects indicating their mildness in hair care products.
Thus, the advantages of the quaternary ammonium compounds of the invention include:
Mildness of the formulations containing the quaternary ammonium compounds
Very low toxicological profile
Low irritation
Impart softer feel and better control of fibers
Thus, the novel quaternary ammonium compounds of this invention have unique properties in that they are mild to the skin, have very low to negligible toxicological effects, and very low eye and skin irritation. These properties make these quaternary ammonium compounds useful as vehicles or carriers, dispersants, emulsifiers, emollients, solubilizers and conditioners for hair care formulations such as hair creams, lotions, as well as other formulations. The foregoing list is only exemplary of the type of compositions in which the quaternary ammonium compounds of this invention may be used, and, as such, is not to be considered limiting.
The amount of such quaternary ammonium compounds to be used in such compositions is dependent on the type of hair care compositions, the desired dosage or amount of active ingredient to be delivered, the type and quantity of other ingredients, such as cosmetic ingredients used, the amount and type of functional additives that are utilized, the user""s skin and hair type, and the severity and extent of the skin or hair condition, and other parameters that will be apparent to those skilled in the art. Generally, compositions containing the quaternary ammonium compounds of the invention are topically applied in effective amounts to the affected areas of the skin or to hair. Typically, the amount of quaternary ammonium compounds used ranges from about 0.5% to 10.0%, by weight, of the formulation.
The quaternary ammonium compounds of the invention have properties such as, being less greasy, less oily, low toxicity, ease of emulsification, acid and alkaline stability, the ability to form gels with suspending agents, water solubility/dispersibility, and the ability to be combined with many common hair care ingredients.
The following are non-limiting examples of processes for preparing the quaternary ammonium compounds compositions of the invention (Examples 1 to 51), comparative substantivity properties (Example 52), comparative conditioning properties (Example 53), and toxicology studies (Example 54). In the Examples, as well as throughout this application, the chemical and scientific symbols have their customary meanings and all percents are weight percents unless otherwise specified.
Example Nos. 1 through 51 identify quaternary ammonium compounds produced by the process of the invention. For ease of identification, each preparation is identified by both an Example Number and a Reference No., where applicable.
Although the Examples use only selected compounds and formulations, it should be understood that the examples are illustrative and not limited. Thus, any of the aforementioned Reactants A and B may be substituted according to the teachings of this invention in the following Examples.